DE2422170C2 - Polymerizable N, N-disubstituted carbamoyloxyalkylcarboxylic acid esters, process for their preparation and their use - Google Patents

Description

Ri and R _{2 are} identical or different and are alkyl with 1-4 C atoms, cycloalkyl with 5-6 C atoms, or Ri and R ₂ together with the nitrogen atom attached to them form a morpholine ring, a piperazine ring or an N-alkylpiperazine ring ( Alkyl with Ci - Cj atoms};

R _{3 is} hydrogen, methyl or ethyl; R »hydrogen or methyl; R _{5 is} hydrogen or methyl or below the

Condition that R »is hydrogen, Rs a carboxy residue (- COOH) mean.

2. Process for the preparation of the polyetherizable Ν, Ν-disubstituted carbamoyloxyalkylcarboxylic acid esters according to claim 1, characterized in that Ν, Ν-disubstituted carbamic acid-ßhydroxyalkyl esters of the general formula II

R, O

N-C-O-CH-CH ₂ OH

wherein

Ki, R2 and R3 have the meaning given in claim 1,

with «^ -monoolefinically unsaturated carboxylic acids with 3-5 carbon atoms or their chlorides, bromides or their anhydrides at temperatures from 0 to - »o 150 ° C, optionally in an organic solvent, in the presence of esterification catalysts and optionally in the presence of Reacts chlorine or hydrogen bromide acceptors.

3. Use of the polymerizable Ν, Ν-disubstituted Carbamyloxyalkylcarbonsäureester according to claim 1 for the preparation of homo- and Copolymers.

The invention relates to polymerizable Ν, Ν-disubstituted carbamoyloxyalkylcarboxylic acid esters, their production and their use for the production of Polymers.

It is known that non-polymerizable Ν, Ν-disubstituted Carbamoyloxyalkylcarbonsäureester (A) by Implementation of carboxylic acid halides and Ν, Ν-disubstituted carbamic acid-ß-hydroxyalkyl esters under the conditions of a Schotten-Baumann reac tion, for example according to the following equation:

Rh

NC-O-CH ₂ -CH ₂ -OH + Cl-CR _c

-HCI

O O

NCO-CH ₂ -CH ₂ -OC-Rc (A)

R ₁ , Rb alkyl; Rc alkyl, aryl (see Bull. Soc Chim, France (1951), pp. 392-396).

The object of the present invention was to provide polymerizable Ν, Ν-disubstituted carbamic acid esters as To provide intermediate products for the production of valuable polymers.

The object was achieved in that polymerizable carboxylic acid chlorides, carboxylic acid anhydrides or Carboxylic acids reacted under esterification conditions, for example under the conditions of a Schotten-Baumann reaction or according to Einhorn with Ν, Ν-disubstituted carbamic acid-j3-hydroxyalkyl esters

will. (VergL Houben-Weyl, Methods of Organic Chemistry (1952), Volume 8, pages 545-549 and Pages 655-658.)

The invention thus relates to polymerizable Ν, Ν-disubstituted carbamoyloxyalkylearboxylic acid esters of the general formula I.

R ₁

OR ₄

NCO-CH-CH ₁ -OCC = CH

wherein

Ri and R _{2 are} identical or different and are alkyl with 1-4 carbon atoms, cycloalkyl with 5-6 carbon atoms, or Rt and R ₂ together with the nitrogen atom attached to them form a morpholine ring, a piperazine ring or an N-alkylpiperazine ring ( Alkyl with Cj - C ₄ atoms); R _{3 is} hydrogen, methyl or ethyl;

R _{4 is} hydrogen or methyl; R _{5 is} hydrogen or methyl or below the

Condition that R _{4 is} hydrogen, Rs is a carboxy radical (- COOH).

In the above formula I, Ri and / or R ₂ preferably denote methyl, ethyl, cyclohexyl or Ri and R ₂ together with the nitrogen atom attached to them denote a morpholine or an N-alkylpiperazine ring with 1-2 C atoms in the alkyl radical R ₃ Hydrogen or methyl, R ₄ hydrogen or methyl, R ₅ hydrogen and if R ₄ hydrogen, R; a carboxy residue

The following compounds may be mentioned as examples:

NN-dimethylcarbamoyloxyäihylacrylat, N, N-diethylcarbamoyloxyäthylaci ^ (at, N-Methyl-N-Cyclohexylcarbamoyioxyäthyl-

acrylate,

Morpholine-4-carboxylato-ethyl acrylate, Piperazine-1-methyl-4-carboxylato-ethyl acrylate as well as the corresponding methacrylates, -crotonate, -monoitacenate and -monomaleinate. The methacrylate compounds are preferred.

The invention also relates to a process for the preparation of the carbamoyloxyalkylcarboxylic acid esters according to general formula I.

The compounds used as starting material, the Ν, Ν-disubstituted carbamic acid - /? - hydroxy alkyl esters of the general formula II:

Ri OR ₃

NCO-CH-CH ₂ -OH (II)

- Ri, R ₂ and R ₃ have the same meaning as in formula I - are known (cf. Bull. Soc. Chim, France [195IJ p. 392-396), or can be carried out analogously to the process given in the aforementioned publication produce.

The esterification of the ß-hydroxyalkyl carbamic acid ester of the formula II with ^ -monoolefinically unsaturated carboxylic acids with 3-5 carbon atoms or their Halides or anhydrides are carried out according to known methods at temperatures from 0 to 150 ° C in Substance or an organic solvent, optionally in the presence of esterification catalysts. As «, ^ - monoolefinically unsaturated carboxylic acids with 3-5 carbon atoms are acrylic acid, methacrylic acid,

Crctonic acid, itaconic acid and maleic acid called als Halides of these acids are chlorides and Bromides, preferably chlorides, are used The esterification is preferably carried out by acyl

tion of the compounds of the formula II with the anhydrides, chlorides or bromides of the "^ -monoolefinically unsaturated carboxylic acids with 3-5 C atoms at temperatures from 0 to 10O ⁰ C in bulk or in solution. Examples of solvents are Methylene chloride, dichloroethane, chloroform, acetone, Mono- and dichlorobenzene, benzene, toluene, nitromethane, dimethylformamide are suitable

If carboxylic acid halides such as carboxylic acid chlorides or bromides, preferably carboxylic acid

jo chloride used so it is recommended in the presence of a hydrogen halide acceptor to work. For this purpose alkali hydroxides, alkali carbonates, alkali acetates, tert amines such as diazabicyclo- [2,2,2] -octane, pyridine, Quinoline, isoquinoline, triethylamine or diethylaniline or their mixtures in question. The hydrogen halide acceptors can be used in the equivalent amount or 1 - 50 times the equivalent amount, based on Carboxylic acid halides can be used. In the case of the use of carboxylic anhydride The acylation in substance or in the above specified solvents take place under the same temperature conditions. No hydrogen halide acceptors are necessary here, although it is often from The advantage of acylation is less in the presence Quantities (up to about 10% by weight, based on anhydride) a tert amine such as pyridine, concentrated sulfuric acid, zinc chloride or alkali acetates. The monomers according to the invention fall if acylation is carried out in substance with carboxylic acid anhydrides, directly and can, if desired, purified by distillation or in some cases from alcohols or Mixtures of aromatic hydrocarbons such as benzene and aliphatic hydrocarbons such as Petroleum ether, to be recrystallized. Will the Acylie tion in solvents with carboxylic acid halides or anhydrides carried out, so the organic Phase isolated, with an aqueous solution of sodium bicarbonate and then with water washed, concentrated and then distilled or be recrystallized.

The monomers according to the invention are new and represent starting materials for homo- and copolymers with valuable properties. The invention also relates to the use preparation of the carbamoyloxyalkylcar according to the invention acid esters for the production of homo- and copolymers. The monomers according to the invention can here

individually or in a mixture with one another or one or several of these monomers with other copolymerizable, ethylenically unsaturated compounds are polymerized.

In the present application, the term copolymerization is understood not only to mean processes which lead to copolymers with a statistical distribution the polymerized monomers or lead to Blockcopoiymerisaten, but also processes where on a pre-formed homo- or copolymer monomers are grafted on. Statistical copolymers are preferred

For the copolymerization with at least one compound of the general formula I, one or several monomers from the following groups can be used:

a) a ^ monoolefins with 2-8 carbon atoms, such as ethylene, Propylene, butene-1, isobutylene, diisobutylene;

b) Conjugated diolefins with 4-6 carbon atoms, such as butadiene, isoprene, 2,3-dimethylbutadiene, 2-chlorobutadiene, preferably butadiene;

c) (meth) acrylic acid, (meth) aerysonitrile, (Methjacrylic acid amide.iMethjacrylic acid alkyl ester with 1 to 18, preferably 1 to 8 carbon atoms in the Alcohol component, such as methyl acrylate, ethyl acrylate, propyl acrylate, isopropyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate, stearyl acrylate or the corresponding methacrylic acid alkyl esters, preferably acrylic acid, acrylonitrile, acrylamide, methyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate;

d) Vinyl esters of organic monocarboxylic acids, the acid component being 1-18, preferably 2-4 Contains carbon atoms, such as vinyl acetate and vinyl propionate, vinyl acetate is preferred;

e) Monoolefinically unsaturated halogenated hydrocarbons, such as vinyl chloride or vinylidene chloride, preferably vinyl chloride;

f) vinyl aromatics such as styrene, o- or p-methylstyrene, Λ-methylstyrene, «-methyl-p-isopropylstyrene, «-Methyl-m-isopropylstyrene, p-chlorostyrene, preferably styrene;

The less readily polymerizable monomers such as-methylstyrene and m- or p-Isopropyl-Ä-methylstyrene, preferably always im Mixture with at least one other of the specified copolymerizable monomers used;

g) Monoesters of -monoolefinically unsaturated monocarboxylic acids with 3 - 4 carbon atoms dihydric saturated aliphatic alcohols having 2-4 carbon atoms, such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate;

h) N-methylol ethers of acrylic acid and methacrylic acid amides of the general formula III

CII ₂ = C-CO-N-CH ₂ -OR ₂ (III) RR ₁

in which R stands for hydrogen or methyl, R for hydrogen, alkyl, aralkyl or aryl, R ₂ for alkyl or cycloalkyl, such as methyl, ethyl, n-propy ¹ , Isopropyl, η-butyl, isobutyl, cyclohexyl (cf. German Auslegeschrift 10 35 363), N-methylol methyl ether of methacrylic acid amide is preferred. The monomers of group h) are in Quantities of 1-20% by weight, based on total monomers, are used and in the copolymer built-in;

i) Di- and monoesters of maleic, fumaric and itaconic acids with 1-18 carbon atoms in the alcohol 'component, also maleic anhydride, maleic or fumaric acid, amides of maleic and fumaric acid, maleimides and unsaturated copolymerizable polyesters, which are used as polymerizable Components the remains of Malein and / or Contain fumaric acid. Maleic anhydride is preferred;

j) vinyl alkyl ethers with 1-4 carbon atoms in the alkyl group, such as vinyl methyl ether, vinyl ethyl ether, Vinyl propyl ether, vinyl butyl ether.

k) Crosslinking monomers with several non-conjugated olefinically unsaturated carbon-carbon bonds such as divinylbenzene, Diallyl phthalate, divinyl adipai, acrylic and / or Allyl methacrylate, methylenebisacrylamide, Methylenebismethacrylamide, triallyl cyanurate, triallyl isocyanurate, triacryloyl perhydro-S-triazine, bisjcrylate or bismethacrylate of glycols or Polyglycols with 2-20 C atoms, such as ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylic

jo lat, butylene glycol 1,4-di (meth) acrylate, tetraethylene glycol di (meth) acrylate, trir (meth) acrylate des Trimethylolpropane or glycerine.

The crosslinking monomers of group k) are

preferably in amounts of 0.1-12% by weight, based on Total monomers used for copolymerization They are used in equal proportions in the copolymer built-in

In addition, it can also be primary, or secondary

tertiary aminoalkyl esters of (methacrylic acid with preferably 2-4 carbon atoms in the alkyl group and glycid (meth) acrylate are used as comonomers and optionally via the amino or epoxy group crosslinked during or after the copolymerization will.

Preference is given to using monomers of groups b), c), d), e), f) and i) for the copolymerization. the Unless stated otherwise, comonomers can be used in amounts of 5 to 95% by weight, preferably 40% by weight

so up to 90% by weight, based on total monomers, are used for the copolymerization. Accordingly, the monomers of the formula I 5-95 are accounted for % By weight, preferably 10 to 60% by weight. In these proportions they are also preferred in the Copolymers are incorporated, in addition to the customary comonomers, also those from groups h) and k) or Still other monomers copolymerizable with the monomers of the formula I are used, so is their under h) and k) specified share in the total share of the comonomers (5 - 95% by weight).

The manufactures .ig the homo- and copolymers can according to the radical or ion chain mechanism in continuous or discontinuous processes take place.

In the case of ionic polymerization, catalysts of the anionic reaction type are preferably used in amounts of 0.01-5% by weight, preferably 0.01-2% by weight, based on total monomers,

used, ζ. B. metal alkyls, alkali metal alcoholates, metal amides or metal hydroxides such as butyllithium, zinc alkyl with 1-4 C atoms in the alkyl groups, lithium alcoholate, kaüum tert-butoxide, sodium amide, or mixed catalysts such as aluminum triethyl titanium IV chloride in aprotic solvents such as z. Dimethylformamide, dimethyl aniline, benzene, toluene, at temperatures of about -80 ⁰ C to about +110 ⁰ C, preferably at -60 ⁰ C to + 10 ° C, optionally under pressure.

The polymerization is preferably carried out according to the radical chain mechanism in the presence of free radicals supplying substances.

Inorganic per compounds such as potassium or ammonium persulfate, hydrogen peroxide, Alkali percarbonates, organic peroxide compounds such as acyl peroxides, for example dibenzoyl peroxide, Dichlorobenzoyl peroxide, di-tert-butyl peroxide, dicumyl peroxide, tert-butyl perbenzoate, alkyl hydroperoxides, such as tert-butyl hydroperoxide. Cumene hydroperoxide. p-menthane hydroperoxide, Percarbonates such as cyclohexyl peroxydicarbonate, diisopropyl peroxydicarbonate, ethylhexyl peroxydicarbonate, also tert-butyl peroctoate, tert-butyl perpivalate or azodiisobutyric acid dinitrile in Consideration. The inorganic or organic per compounds can also be used in combination with Reducing agents can be used in a manner known per se. Suitable reducing agents are, for example Sodium pyrosulfite or bisulfite, sulfinates, iron (II) salts, cobalt naphthenate, ascorbic acid, aromatic Amines such as p-toluidine.

There are also metal complexes such as acetylacetonates of manganese and cobalt and diacyl peroxide / tertiary amine system suitable. However, elevated temperatures, light and energy-rich rays can also polymerize trigger.

The copolymerization with radical-forming substances such as azodiisobutyric acid dinitrile is preferred, Benzoyl peroxide, tert-butyl perbenzoate and potassium persulfate carried out.

The amount of catalyst that can be considered is within that which is usually suitable Limits, i.e. between about 0.01-5% by weight, preferably 0.01-2% by weight, calculated on the total used monomers.

The polymerization can be carried out at temperatures of - 20 to 16O ⁰ C, preferably from 40 to 110 ° C, optionally carried out under pressure, after the usual methods of bulk, solution, precipitation, dispersion, emulsion, or bead polymerization . Bulk, solution and emulsion polymerization, in particular solution polymerization, are preferred.

When polymerizing in solution, common solvents such as halogenated ones are used Hydrocarbons, for example methylene chloride, trichlorethylene, tetrachloroethane, ketones such as acetone, Methyl ethyl ketone, esters such as ethyl-bis-octyl acetate, Ethyl glycol acetate, methyl glycol acetate, ethylene glycol mono- or bis-methyl ether, diethylene glycol mono- or bis-methyl ether, aromatic hydrocarbons such as toluene, benzene, xylene, dichlorobenzene and Trichlorobenzene. To isolate them, the high polymers can either be stripped with steam or be precipitated in a non-solvent such as petroleum, gasoline, petroleum ether, methanol, or diethyl ether.

The precipitation polymerization is expediently carried out in a good solvent for the monomer, but in which the polymer is insoluble such as in toluene.

The dispersion or bead polymerization is carried out in an aqueous liquor in the presence of the customary protective colloids such as methyl cellulose, gelatin, saponified polyvinyl acetate, styrene-maleic anhydride polymers, precipitated > tem calcium phosphate, or aluminum hydroxy gels carried out. Additional buffer substances can be used such as sodium carbonate, primary, secondary or tertiary sodium phosphate, alkali borates can be added. For controlling of the particle diameter, foreign salts such as

ίο Sodium sulfate or alcohols such as butanol in Amounts from 0.1 to 2% by weight. based on monomers, be present.

The particle diameter can also be determined by using surface-active substances

ι ι like fatty alcohol sulfonates or started on phenols Regulate polyethylene oxides (reaction products of phenols with ethylene oxide) etc.

The homopolymerization and copolymerization of the monomers according to the invention can be carried out in fipgpnwart vnn Q.! hjc 2

.'η% by weight, based on total monomers of a molecular weight regulator take place. Mercaptans such as tert-dodecyl mercaptan, xanthates, thioglycerol can be used as such or nitrotoluenes, cumene, halogen derivatives such as carbon tetrachloride, haloforms such as chloroform or

r> methyl vinyl carbinol, isopropanol, allyl alcohol, etc. be used.

The homopolymers and copolymers of monomers prepared with the erfindungsgi "Maessen monomers can have from about 5000 10 ⁷ molecular weights.

jo The polymers according to the invention can find a wide range of industrial uses, for. B. to Production of shaped structures, such as moldings, coatings or adhesives, as binders for Nonwovens and paper coating slips, as textile, leather

j5 and paper auxiliaries or finishing agents.

It is particularly surprising that the invention Polymers show a strong affinity for polymers containing hydroxide groups, without a to exhibit remarkable basicity. This property has above all when the polymers are used for the refinement of cellulose-containing materials of great technical interest.

The percentages and parts given in the examples relate to weight, if not otherwise noted.

Starting products

The preparation of the N, N-disubstituted carbamic acid-ß-hydroxyalkyl ester used as starting material can after the in Bull. Soc. Chim. France (1951), pp. 392-396, or the general regulation below:

To 1 mole of cyclic glycol carbonate melted at 40 ° C., for example ethylene carbonate (melting point 39-40 ° C.), approx. 1.1-1.2 moles of sea are slowly added with cooling at f = 20-40 ° C. Amine added dropwise over the course of 30 minutes or, in the case of gaseous amines (dimethylamine), passed through. The reaction mixture is stirred for 5 hours at 40 ^° C. and then fractionally distilled in an oil pump vacuum. The boiling points or melting points of the Ν, Ν'-disubstituted carbamic acid - /? - hydroxyalkyl esters are given in the following table. Elemental analyzes were carried out for all the compounds listed, with the values found agreeing with the theoretical values within the error limits. The purity of the compounds was also checked by gas chromatography

N, N- disubstituted amic acid-y-methyl-hydroxy-ethyl-cylcler O

Il

X -C-OCH, -CH ₁ -OH bp ("C)
(hi -v torr)

X = --Ν

CH ₃

CH ₃

N.N-Dimethylcarbamic acid ^ / f-hydroxyiithyl ester 77-79 (0.2 torr)

Irelhan

C ₂ H ₅

X = - N 75 (0.1 torr)

C ₂ H ₅ NN-dimethylcarbamic acid jJ-hydroxyethyl ester

CH ₂ -CH ₂ -CH ₂ -CH ₃

X = --Ν

CH ₂ -CH ₂ -CH ₂ -CH ₃

N.N-diethylcarbamic acid - ^ - hydroxyethyl ester 91 (0.5 torr)

X = —N

CH ₃

N-methyl-N-cyclohexylcarbamic acid ^ -hydroxyethyl ester 147 (0.3 Torr)

X = -N O

Morpholine-4-carboxylic acid-jS-hydroxyethyl ester 120 (0.15 Torr)
(Fp .: 49-50 ⁰ C)

X = -N 'N-CH ₃ 128 (0.2 torr)

Piperazifi-1-methyl-4-carboxylic acid, 8-hydroxyethyl ester

N.N-disubstiUiiertc OirbamiiKiure- / f-hy <lrnxyl-mclhyl-iilhylcslcr

O CII,

Il I

X — C — OCH, —CH. OH bp ( ⁰ C)
(at v Torr)

llrelhiin

CH ₃

X = - Ν

CH.,

Ν, Ν-dimethylcarbamic acid-yi-hydroxy-1-methylethyl ester

(0.5 torr)

CH ₂ -CH ₃

X = —N

CH ₂ -CH ₃

Ν, Ν-diethylcarbamic acid ^ / f-hydroxy-1-methylethyl ester

74 (0.1 torr)

X = —N

N-CH ₃ 128 (0.3 torr)

Piperazine-1-methyl-4-carboxylic acid _: / i-hydroxy-I-methylethyl ester

Examples

The monomers according to the invention can be obtained according to the following general procedure:

Under a constant stream of nitrogen, about - 1.1-1.2 mol of the "^ -unsaturated carboxylic acid chlorides given in the table below are converted into a mixture of 1 mol of the stated carmidic acid /? - hydroxyalkyl ester and 500 cm ^{3 of} acetone. 1.5 mol diazabicyclo [2,2,2] octane, and 5 grams of phenothiazine in the course of 1 -2 hours at 10-30 ⁰ C and then added dropwise at about 40 "C 5 - After stirring for 20 hours. When the reaction is complete, the hydrochloride of the diaza-bicyclo- [2,2,2] -octane is filtered off with suction and washed with acetone. The filtrate is stabilized with about 90-500 mg * 1 methylene blue and concentrated on a rotary evaporator , 2,2] -octane hydrochloride is extracted with ice water in a separating funnel and neutralized with sodium hydrogen carbonate. After the organic phase has been separated and dried, fractional distillation is carried out in an oil pump vacuum. Yields and refractive indices:

If the corresponding anhydrides, in particular maleic anhydride, are used instead of the <x ^ -unsaturated carboxylic acid chlorides, this is successful; entering and stirring of the anhydride conveniently at about 70 ⁰ C.

The following components were used in the examples:

example 1
Example 2
Example 3
Example 4
Example 5
Example 6
Example 7
Example 8
Example 9
Example 10

Methacrylic acid chloride

Methacrylic acid chloride

Methacrylic acid chloride

Methacrylic acid chloride

Methacrylic acid chloride

Methacrylic bromide

Methacrylic acid chloride

Methacrylic acid chloride

Maleic anhydride

Acrylic acid chloride

+ Urethane A + urethane B + urethane C + urethane D + urethane E + urethane G + Urethane H + urethane I + urethane A + urethane A

Initial

At · end product
game

Formula of the final product

the end
prey Kp. ( ⁰ C) Refractive
index rip ' Purity*
Degree iWeight%) (at ν Torr) (%) 30th 88-90
(0.2 torr) 1.4512 97-99 79 90
(0.2 torr) 1.4491 98-99 75 140
(0.2 Torr) 1.4741 97

Ν, Ν-dimethylcarbamoyloxyethyl methacrylate

2 Ν, Ν-Diiithylcarbamoyloxyäthylmcthacrylat

3 N-methyl-N-ryclohexyl-

carbamoyloxyülhylmelhacryhit

4 Morpholine-4-carboxylatoethyl methacrylate

S pipcrazin-1-methyl-

4-earboxylatoä thy Imethacry Int

6 Ν, Ν-dimethylcarbamoyloxy-I-methylethy Imethacry lat

7 Ν, Ν-diethylcarbamoyloxy-1-methylethyl methacrylate

(CHj) ₂ N-COO (CH ₂ ^ -OOC-C = CH ₂

CH ₁ (C ₂ Hs) ₂ N-COO (CH ₂ J ₂ -OOC-C = CH ₂

CH ₃ CH, - N -COO (C Hj) ₂ - OOC - C = CH ₃

CH,

θ "N-COO (CH ₂ I ₂ -OOC-C = CH: 67

CH ₃

CH ₃ -NN -COO (CH ₂ ) ₂ -OOC-C = CH ₂ : 56

O CH ₃ O CH ₃

(CHj) ₂ N-CO-CH-CH ₂ -OCC = CH ₂ 60

O CH ₃ O CH ₃

Il Γ Il!

(C ₂ Hj) ₂ NCO-CH-CHj-OCC = CH ₂ (SO

110

(0.3 Torr)

(Fp .: 40 ⁰ C)

140

(0.4 Torr)

132

(0.2 torr)

95

(0.22 torr)

82-84
(0.05 torr)

97

1.4803 99-99.9

98-99

97

15th

! ε -ο

5 « a! Ä

S.

β B

-α

Ul

-

OO

fc υ

O ο

^Μ - ^

2S £

O OO

X 33 33 O U- U
Il 53 *
"Υ O
U Il
X χ Il I. U U-U X I. I. U I. O = U Il U I. Il ο ο X O I. U I. 53 I. U U X I. O U X X O I. U-U I. X I. -U O
I. ac I. O = U U ο I. δ O Z ο υ
I. O U ζ Z ζ I. 53 3? 33 U U U

S ■ e «

JO

JC υ

ε U _-

ο. ε ^ζ . ο

ε ^ ζ ε

The purity of the substances was checked by gas chromatography and elemental analysis The values found in the elemental analyzes of all the compounds indicated agreed with the theoretical ones matched well and were within the permissible error limits.

Use for the production of homopolymers

Examples IbisIV

There are the monomers listed in Table 1 in amounts of 0.1 MoI in 100 ml of distilled toluene with those given in the Table II initiator concentrations under nitrogen at 60 ⁰ C polymerised The polymerization time is about 5-10 hours. After termination with an inhibitor (such as hydroquinone), it is usually precipitated in petrochemical or diethyl ether and dried

The molecular weights (Mgpc) of the polymers obtained were determined by means of gel permeation chromatography measured (cf. J. C Moore, J. Polymer Sei, A-2 (1964), p. 835). The degrees of polymerization range between 200 and 2000.

The end groups of the polymer chains are generally either monomer units or initiator residues, or residues of carrier molecules. Details are given in Table II.

5-S

S?

Ι «-ε &

CU

Έ "Ξ.

230 238/159

Table II Recurring unit in the polymer

Ester yield concentration Idl / g] Mc pe 10 ⁵ used Poly of azodiiso- 10 ⁵ merisat butyric acid 0.127 10 ⁵ nitrile 0.15 10 ⁵ (G) (Wt .-%) (Mole / mole 0.235 Monomer) 0.64 20.1 92.6 0.1 [DMF] 0.52 90 0.05 0.74 89 0.01 1.50 - 61.5 0.001 5.20 ·

CHj

CH ₂ -C-

CH ₂ -C-

C = O O

I Il

O (CHj) ₂ OC-N (CHj) ₂

CH ₃

22.9 93

0.01

0.27

2.0 · 10 ⁵

CH ₂ -C-

C = O

I Il

Q (CHj) ₂ OC-

CH ₃

26.9

89

0.01

0.232 [THF]

2.43 ■ 10 ⁵

C = OO CH ₃

I Il I

0 (CHj) ₂ OCN

CH ₃

CH ₂ -C-

24.3

90

0.01

C = O O

I Il

Q (CH ₂ ) JO-CN

0.197 [THF]

1.22 · 10 ⁵

DMF = dimethylformamide. THF = tetrahydrofuran.

[i, | = Intrinsic viscosity at / = 25 ° C.

π - 200-2000.

In the following examples V to VH, the in the monomers used in Examples I to IV in aqueous emulsion or with the aid of other initiators or subjected to homopolymerization in other solvents.

Example V

In 100 ml of distilled, boiled water wi 23 g of sodium auryl sulfate as an emulsifier and 20.1 g N.N-diethylcarbamoyloxyäthylmethacrylat added. After purging with nitrogen, 270 mg of potassium persulfate are added and the mixture is left at 60 ° C. for several hours polymerize a conversion above 95%. The polymer is in the warm with a 5% aqueous Sodium chloride solution precipitated. A polymer with a molecular weight of 1.4 · 10 ′ is obtained.

Example Vl

20.1 g of Ν, Ν-dimethylcarbamoyloxyethyl methacrylate are mixed with 100 ml of distilled toluene under nitrogen. Then 242 mg of dibenzoyl peroxide are added and polymerization is carried out at 60 ° C. After about 5 hours, the polymerization is terminated at a conversion of about 70% and the polymer with Petroleum ether precipitated The molecular weight was measured - as in all examples - by means of gel permeation chromatography and was 4.0 · 10A

The intrinsic viscosity [η] was determined to be 0.45 [dl / g] in DMF at r = 25 "C.

Example VII

20.1 g of N, N-dimethylcarbamoyloxyethyl methacrylate and 16.4 mg are dissolved in 100 ml of pure dioxane

Azodiisobutyronitrile is added 5 hours at 60 ⁰ C polymerized terminated at a conversion of about 85% and precipitated with petroleum ether or ether

The intrinsic viscosity [η] = 0.362 (dl / g) was determined at i = r 25 ° C., the molecular weight was 10 ⁵ .

Use for the production of copolymers Examples VIII through XJV Example VIII

52 g of distilled styrene is charged under nitrogen with 100.5 g Ν, Ν-Dimethylcarbamoyloxyäthylmethacrylat in a pressure bottle blended Then 164 mg of azodiisobutyronitrile were added and polymerized at 60 ⁰ C is about 5 hours polymerized up to a conversion of 80% and in c Petroleum ether or ether precipitated The copolymer contained copo-

Polymerized units of 353% by weight of styrene and 64.1% by weight of Ν, Ν-dimethylcarbamoyloxyethyl methacrylate. The intrinsic viscosity [η] of the copolymer was 0.40 (dl / g) in DMF at f = 25 ° C

Example IX

20.1 g of N.N-dimethylcarbamoyloxyethyl methacrylate is mixed with in each case 0.1 mol of the comonomers mentioned in Table III in 100 ml of toluene. Thereafter 328 mg of azodiisobutyronitrile are added and polymerization is carried out at 60 ° C. After about 5-10 hours the reaction is terminated and precipitated in petroleum ether or ether. If desired, the conversion can through Increase in initiator rate increased to 95-99% will. The [η] values were in DMF at 25 ° C determined The content of built-in N, N-dimethyl-carbamoyloxyethyl methacrylate results from the Difference 100- incorporated comonomer.

Table III Amount in sales Comonomer w [f J Comonomer lsi |% I built-in in DMF !% By weight) 0.45 10.4 70 36.0 - Styrene 8.6 70 22.4 0.369 Vinyl acetate 8.6 90 30.0 - Acrylic acid methyl ester 10.0 68 29.0 Methacrylic acid methyl ester 5.4 60 24.8 XI Butadic.i example

20.1 g of NN-dimethylcarbamoyloxyethyl methacrylate and 53 g of acrylonitrile are dissolved in 100 ml of N, N-dimethylformamide. Then 328 mg of azodiisobutylronitrile are added and polymerized at 60 ° C. under nitrogen. After 21 hours, the conversion was 81%. The polymer is precipitated with ether and dried. The copolymer is composed of 42.4% by weight of copolymerized units of Ν, Ν-dimethylcarbamoyloxyethyl methacrylate and 57.6% by weight of acrylonitrile. The intrinsic viscosity [η \ measured in DMF at f = 25 ° C is 0.71 [dl / g].

10.4 g of styrene are each 0.1 mol of the in Table IV Listed polymerizable N, N-disubstituted carbamic acid esters dissolved in 100 ml of toluene Then the amounts of azodiisobutyronitrile indicated in Table IV are added and the mixture is heated at 60.degree polymerized. After approx. 10-20 hours the reaction is terminated and the polymer is dissolved in petroleum ether precipitated By increasing the amount of initiator, the Sales can be increased to over 90%. From Table IV further details can be seen. The percentages of built-in styrene result from the difference 100 - built-in carbamic acid ester.

Table IV

Polymerizable carbamic acid esters formula

Copolymer

used initiator sales Amount in

Carbamide

ester

units

[% By weight |

CH ₃ CH ₂ = CC = OOC ₂ H ₅

0 (CH ₂ J ₂ OCN

\ C ₂ H ₅

22.9

328

63.4

0.1289

continuation

Polymerizable carbamic acid esters Pormel

Copolymer

used initiator conversion carbamic! - [i ₍ ] amount in ester

units

[mg]

[% By weight] [dl / gj

CH ₃

CH ₂ = CC = O

I Il

0 (CH ₂ ^ OCN N-CH ₃

26.9 164 63.5 66.1 0.1766

24.3 164 79.5 7t \ 4

25.6 164 71

73.2

Example XII

25.6 g of piperazine-1-methyl-4-carboxylato-ethyl methacrylate are dissolved in 500 ml of boiled water. Then enough 80% nitric acid is added until a pH 6 is reached. Then 56.8 g acrylamide and 7.2 g acrylic acid are added as well as 50 ml isopropanol to regulate the molecular weight. 400 mg of potassium persulfate are added as initiator. The polymerization is carried out at <= 80 ° C. for a period of 3 hours. The water-soluble polymer is precipitated in methanol and dried. The intrinsic viscosity [η] in carbon tetrachloride is 1.18 [dl / g]. The copolymer consists of copolymerized units of 29% by weight. Piperazine-1-methyl-carboxylato-ethyl methacrylate, 63% by weight of acrylamide and 8% by weight of acrylic acid. The yield was 85% by weight.

Example XIIl

27.0 g of piperazine-l-methyl-4-carboxylato [1-methyläthylmethacrylat] are mixed in 100 ml of distilled, dry toluene with 10.4 g of styrene and, after addition of 164 mg of azodiisobutyronitrile polymerized at 6O ⁰ C within 10 hours. Then it is precipitated in petroleum ether. The conversion is 70%. The copolymer is composed of 54% by weight of piperazine-1-methyl-4- 60 60 ⁰ SR carboxylato [1 -methylethyl methacrylate] units and 46% by weight of styrene units built up The intrinsic viscosity [> /] in DMF at i = 25 ° C is 0.162 [dl / g}

Example XIV

65 g of acrylamide and 10 g of piperazine-1-methyl-4-carboxylatoethyl methacrylate are boiled in 1150 g Submitted tem distilled water and adjusted to pH 6 with concentrated hydrochloric acid 10 mg Aminoethyl methacrylate hydrochloride in 12 ml of water are added and then 25 mg of potassium peroxodisulfate in 12.5 ml of water at a constant A polymerization temperature of 25 ° C. was added dropwise. After 24 hours, the same amounts were again added Persulfate and amine hydrochloride metered in. Polymerization takes place for a total of 48 hours. The polymer solution is with 6% aqueous sodium chloride solution

such a 2% solution, based on the polymer, diluted. The viscosity of this solution was 2500 cP. In the sample as a drainage aid, the following MtM degrees at various concentrations c der were determined by the Schopper-Riegler method 2% polymer solution, based on the solid pulp, determined.

Zero value

e = 0.16%

c = 0.32%

0.48%

38 ° SR

55 ° SR

52 ° SR

Claims (1)

Claims; 1. Polymerizable Ν, Ν-disubstituted carbamoyloxyalkylcarboxylic acid esters of the general formula I R, OR ₃ OR ₄ R ₅ \ Il I Il I I N - CO-CH-CH ₂ -OCC = CH worm